CN101016651A - Annealed wafer and manufacturing method of annealed wafer - Google Patents

Annealed wafer and manufacturing method of annealed wafer Download PDF

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CN101016651A
CN101016651A CNA2006101725314A CN200610172531A CN101016651A CN 101016651 A CN101016651 A CN 101016651A CN A2006101725314 A CNA2006101725314 A CN A2006101725314A CN 200610172531 A CN200610172531 A CN 200610172531A CN 101016651 A CN101016651 A CN 101016651A
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中居克彦
福原浩二
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Siltronic AG
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Abstract

A nitrogen-doped silicon single crystal substrate pulled at the cooling rate of 4 DEG C./minute or more during crystal growth between 1100 and 1000 DEG C. wherein the nitrogen concentration is 1x10<14 >to 5x10<15 >atoms/cm<3 >and V/G satisfies predetermined conditions serves as a substrate, and the substrate is subjected to heat treatment in a non-oxidative atmosphere.

Description

The manufacture method of annealed wafer and annealed wafer
Technical field
The present invention relates to the manufacture method of a kind of annealed wafer and this annealed wafer.
Background technology
Semiconductor substrate, particularly silicon single-crystal wafer (hereinafter still abbreviating " base material " as) are used as the base material of the highly integrated MOS device of manufacturing.Many silicon single-crystal wafers are the base materials that obtain by the silicon single crystal ingot that cutting is made by Czochralski (CZ) method.
In these silicon single-crystal wafers, the oxygen of introducing at the monocrystalline production period exists in the mode of supersaturation concentration.Oxygen is separated out in subsequent device processing, and forms the oxygen precipitate in base material.When capacity oxygen precipitate appeared in the base material, precipitate was absorbed heavy metal, and they are introduced in the base material during device fabrication, and had the effect of maintenance as the substrate surface cleaning of device active layers.
A kind of technology that obtains this effect is known as intrinsic and absorbs (IG), and is used to the characteristic degradation that prevents that heavy metal contamination from causing.Therefore, need to produce suitable oxygen degree of separating out in the device fabrication process in the silicon single-crystal base material.
In order to ensure the absorption ability, the oxygen precipitate of predetermined density or bigger density must be present in the center of silicon single-crystal wafer thickness.By the result of past test as can be known: when guaranteeing every cm 35 * 10 8Or more oxygen precipitate is when the mid-depth of silicon single-crystal wafer, even for also obtaining in the thermal treatment of absorption ability in cryogenic device processing such as the heavy metal of Fe, Ni and Cu, top temperature is equal to or less than 1100 ℃ in this cryogenic device processing.
Simultaneously, the silicon semiconductor substrate that obtains by high-temperature heat treatment (being called " annealing " hereinafter) silicon single-crystal wafer (being called " annealed wafer " hereinafter) is widely used in making the integrated device of high-density height.
At this, before transmission, be known as " minute surface wafer ", and the base material before implementing annealing is known as " base material ", so that they are distinguished mutually without annealed silicon single-crystal wafer.
Known annealed wafer does not have primary defective on substrate surface, as COP (crystal primary particle), and have good device property, for example GOI (gate oxide integrity) characteristic.This is because the primary defective that is present in substrate surface is shunk by high temperature annealing or disappeared, therefore in several microns from the surface zone formation do not contain defective layer.
Yet also known and aforesaid do not have the minute surface wafer of epitaxial deposition to compare, and annealed wafer also has relatively poor absorption characteristic.A kind of possible reason is: usually the oxygen of the nuclear of separating out as oxygen is separated out nuclear owing to anneal and disappear under 1100 ℃ or higher temperature, so afterwards oxygen does not take place in the device fabrication process and separate out.
The someone proposes to be used for compensating in the annealed wafer oxygen and separates out insufficient method, for example uses the manufacture method (referring to following patent documentation 1 and 2) of nitrating base material as the annealed wafer of base material.
This is because when doping nitrogen, during crystal growth, form heat-staple oxygen and separate out nuclear, even and they in annealing steps, do not shrink yet or disappear; Therefore, in device thermal treatment, separate out nuclear after the annealing and produce the oxygen precipitate based on these oxygen.When these base materials were used as base material, the oxygen after can guaranteeing to anneal was separated out.
Yet, because the diameter of present annealed wafer rises to 300mm from 200mm, so the new demand that oxygen is separated out characteristic occurred.This requirement is that the oxygen precipitate density in the control substrate plane keeps evenly.Its reason is: if there is the low density position of oxygen precipitate in the substrate plane, then absorption ability herein can die down, and this will cause the deterioration of device yield.In order to make oxygen precipitate density uniform annealing wafer in the plane, nitrating crystalline growth conditions must accurately be controlled.In routine techniques, do not consider nitrating crystalline growth conditions.Therefore, the annealed wafer by these technology manufacturings can't address this problem, and separates out low density position (referring to following patent documentation 3 and 4) because produced oxygen in substrate plane.
And oxygen is separated out the manufacture method (referring to following patent documentation 5 and 6) of density uniform annealing wafer in the plane.Japanese patent application Te Open 2003-59932 discloses a kind of method, wherein a crystal extensograph parameter V/G is adjusted in certain scope, makes whole base material become the specific region that is known as the OSF zone.And Japanese patent application Te Open 2003-243404 discloses a kind of manufacture method, wherein crystal extensograph parameter V/G is decreased to more than or equal to 0.175 and smaller or equal in 0.225 the scope.Yet, in these methods, because crystal extensograph parameter V/G is limited in the extremely narrow scope, the difficulty that becomes so the control crystal stretches, this is the factor that output reduces.Particularly, the problem of existence is: because stipulated the upper limit of crystal rate of extension, so rate of extension can't improve fully, thereby reduced output.
As mentioned above, it is difficult making the high and annealed wafer that the oxygen precipitate is evenly distributed in substrate plane of oxygen precipitate density.
[patent documentation 1] Japanese patent application Te Open 2000-26196
The flat 10-98047 of [patent documentation 2] Japanese patent application Te Open
[patent documentation 3] Japanese patent application Te Open 2000-26196
The flat 10-98047 of [patent documentation 4] Japanese patent application Te Open
[patent documentation 5] Japanese patent application Te Open 2003-59932
[patent documentation 6] Japanese patent application Te Open 2003-243404
Summary of the invention
The object of the present invention is to provide a kind of annealed wafer, wherein to separate out the radial distribution of enough height and oxygen precipitate density even for the oxygen after annealing, and the manufacture method of this annealed wafer.
The present inventor has carried out extensive studies to the manufacture method of the annealed wafer that do not have above-mentioned routine techniques problem, and wherein to separate out the radial distribution of enough height and oxygen precipitate density even for the oxygen after the annealing.The result is, in view of the radial distribution of oxygen precipitate and nitrating crystal growth condition wherein need the base material defect area that be controlled closely related, the present inventor finds that the radial distribution of oxygen precipitate can become evenly by the crystal growth condition of optimally controlling such as V/G in the growth of nitrating crystalline, and finishes the present invention.
Particularly, the present invention relates to (1) has the layer that do not contain surface imperfection and excellent absorption ability in the entire wafer surface annealed wafer, wherein the minimum value of oxygen precipitate density is 5 * 10 in this annealed wafer plane 8/ cm 3Or higher, and the radially-arranged deviation of oxygen precipitate density is 0.5 or littler.
The invention still further relates to (2) and make the method for annealed wafer, it comprises annealing silicon single-crystal base material, and this base material does not comprise V zone as defect area, and (volume density that is of a size of 50nm or higher hole is 1 * 10 5/ cm 3Or higher zone) and (density that is of a size of 1 μ m or higher dislocation pit is 10/cm in the I zone 2And do not comprise the hole and be of a size of 50nm to 150nm and hole density or higher zone), more than or equal to 10 4/ cm 3And smaller or equal to 10 5/ cm 3The zone.
In addition, the present invention relates to the method that (3) are used for making the annealed wafer described in (2), wherein silicon single-crystal is grown in the following scope as crystal growth condition during by Czochralski manufactured silicon single-crystal: V/G higher limit (mm 2/ ℃ minute) be 1.6 * exp (1.0 * 10 -15* nitrogen concentration (atom/cm 3)) * (V/G) standard, and V/G lower value (mm 2/ ℃ minute) be exp (7.1 * 10 -16* nitrogen concentration (atom/cm 3)) * (V/G) standard is (wherein, V is rate of extension (mm/ minute), G be on the crystal growth direction of principal axis the average temperature gradient from fusing point to 1350 ℃ (℃/mm), (V/G) standard is the lower value that does not comprise as the V/G in the I zone of the defect area in the silicon single-crystal of nitrogen of not mixing, and wherein the I zone is following zone: interstitial atom excessive during crystal growth is introduced this zone and produced the dislocation pit from solid-liquid interface);
From the silicon single-crystal cutting of the growth of this nitrating base material down, the nitrogen concentration in this silicon single-crystal is more than or equal to 1 * 10 14Atom/cm 3And smaller or equal to 5 * 10 15Atom/cm 3, and as base material; And
To this base material impurity concentration smaller or equal to the rare gas of 5ppm in or in nonoxidizing atmosphere in more than or equal to 1150 ℃ and implement thermal treatments more than or equal to 10 minutes and smaller or equal to 2 hours smaller or equal to 1250 ℃, the thickness of sull is controlled in smaller or equal to 2nm after thermal treatment in this nonoxidizing atmosphere.
The invention still further relates to (4) and be used for making the method for annealed wafer described in (3), wherein by the crystal growth condition during the Czochralski manufactured silicon single-crystal be: 1100 to 1000 ℃ rate of cooling is 4 ℃/minute or faster.
Manufacturing method according to the invention can need not to improve and used according to the conventional silicon single-crystal manufacturing equipment of CZ method, and need not to implement complicated manufacturing process; Therefore, under the situation that can significantly not raise the cost, can stably supply high-quality silicon semiconductor substrate.
In addition, according to the present invention, can provide the annealed wafer that does not have oxygen precipitate ununiformity and device performance excellence.In addition, this annealed wafer is the base material of optimum that is used to make the base material of the MOS device that requires high integrity and high reliability.
Description of drawings
Fig. 1 (a) and 1 (b) are used for explaining defect area and according to the synoptic diagram that concerns between the CZ method tensile silicon ingot nitrogen concentration.At this, Fig. 1 (a) is presented at the figure that concerns between the defect area that is present in before the epitaxial deposition in the base material and the nitrogen concentration, and Fig. 1 (b) is presented at the synoptic diagram that concerns between the defect area in the silicon wafer ingot and nitrogen concentration profile during the stretching.
Fig. 2 (a) shows the figure that concerns between nitrogen concentration and the V/G, and Fig. 2 (b) is presented at the interior oxygen of substrate plane to separate out radially-arranged chart, has shown also whether oxygen precipitate density is equal to or higher than 5 * 10 8Atom/cm 3, and whether oxygen precipitate density radial distribution deviation is equal to or less than 0.5.
Fig. 3 (a) and 3 (b) are used to explain make the wherein synoptic diagram of the condition of oxygen precipitate uniform annealing wafer.Fig. 3 (a) shows the figure that concerns between nitrogen concentration and the V/G, and Fig. 3 (b) is presented at the chart that the oxygen precipitate distributes in the substrate plane, has shown also whether oxygen precipitate density is 5 * 10 8Atom/cm 3, and whether oxygen precipitate density radial distribution is equal to or less than 0.5.
Fig. 4 (a) and 4 (b) are used to explain the synoptic diagram that distributes in the plane of the radial distribution in hole and oxygen precipitate.Fig. 4 (a) shows the figure that concerns between nitrogen concentration and the V/G, and Fig. 4 (b) comprises the figure that shows the hole density result, and these holes are directly upwards measured at base material in A, B and C zone respectively and are of a size of 50 to 150nm.
Embodiment
Set forth below and be used to implement optimum specific embodiments of the present invention.
At first elaboration is used to reach the radially inhomogeneity crystal manufacture method of oxygen precipitate.
Use the oxygen precipitate density of the annealed wafer of nitrating base material to depend on nitrogen concentration; And nitrogen concentration is high more, and then oxygen precipitate density is high more.This is because when doping nitrogen, separates out nuclear even form at high temperature still stable oxygen in base material, and they can not disappear and still keep after annealing.Keep oxygen therein and separate out in the annealed wafer of nuclear, in the heat treatment step of following device, form the oxygen precipitate.Even separating out the number of nuclear, at high temperature still stable oxygen depends on nitrogen concentration.Therefore, when nitrogen concentration increased, oxygen precipitate density also increased.At nitrogen concentration is 5 * 10 14Atom/cm 3Or when higher, oxygen precipitate density becomes 5 * 10 8/ cm 3Therefore, even in cryogenic device processing thermal treatment, guarantee that also wherein top temperature is smaller or equal to 1100 ℃ such as the absorption ability of the heavy metal of Fe, Ni and Cu.
The result who studies in great detail is, for the radial distribution of oxygen precipitate obtains following index.Particularly, when being the oxygen of the measurement in the radial direction precipitate density of annealed wafer, and the oxygen precipitate density radial distribution deviation of representing in following expression formula surpasses at 0.5 o'clock, descends and becomes remarkable by absorbing the not enough device yield that causes.The radial distribution deviation of oxygen precipitate density can obtain by following expression formula.
Oxygen precipitate density radial distribution deviation=(oxygen precipitate density maximum value-oxygen precipitate density minimum value)/oxygen precipitate density maximum value
During oxygen precipitate radial distribution after the thermal treatment of at length studying annealed wafer, wherein use the nitrating base material, find to exist oxygen precipitate density to be lower than the position of peripheral region as base material.When observing oxygen precipitate densimetric curve, this part Xiangshan paddy equally sinks.Therefore, these low density zones of oxygen precipitate are known as and separate out the paddy zone hereinafter.When the paddy zone was separated out in existence, oxygen precipitate radial missing degree became 0.5 or bigger.
Discovery is under the situation of using nitrating crystalline annealed wafer, and it is approaching corresponding to defect area that this separates out the paddy zone.This means that when crystal diameter increases to 300mm the defect area in the control crystallographic plane becomes difficult, and the radial distribution of oxygen precipitate density also becomes inhomogeneous, because the outside and inner rate of cooling during crystal growth of crystalline is different.
Hereinafter, after the relation and the defect area in the base material set forth between nitrogen concentration and the V/G, with the relation between the defect area of separating out paddy zone and base material of elaboration annealed wafer.
Fig. 1 (a) and 1 (b) are used for explaining the synoptic diagram that concerns between the defect area of silicon ingot and the nitrogen concentration, and this silicon ingot is according to Czochralski (CZ) method tensile.Fig. 1 (a) shows to be present in the figure that concerns as between defect area in the base material of base material before the annealing and the nitrogen concentration, and Fig. 1 (b) shows the synoptic diagram that concerns between defect area in the silicon wafer ingot 200 and the nitrogen concentration profile during stretching.
In the CZ method, well-known single crystal rod 200 is being grown during pull-up gradually from molten silicon 201.Then, in the base material that obtains by cutting ingot 200, shown in Fig. 1 (a), there are three kinds of defect areas (V zone, OSF zone and I zone).
The V zone is following zone: introduce excessive room from solid-liquid interface to this zone during crystal growth, and wherein have the hole that is formed by the atom vacancy gathering.
The OSF zone is the zone that wherein produces OSF when the silicon single-crystal wafer is implemented oxidizing thermal treatment.At this, OSF is that diameter is about several microns discoid stacking fault, and wherein oxygen precipitate (OSF nuclear) is present in its center.During implementing oxidizing thermal treatment, the interstitial atom that produces from sull/silicon boundary when assembling around the OSF nuclear, forms OSF.In the oxygen precipitate, OSF nuclear is to have the special oxygen precipitate of collecting the interstitial atom characteristic, and they may form in base material after crystal growth immediately.Because the size little (may be 10nm or littler) of OSF nuclear is so can't find them by the existing evaluation measures such as impurity measurement and infrared tomography.Therefore, when implementing oxidizing thermal treatment, determined the existence of OSF first.
The I zone is following zone: introduce excessive interstitial atom from solid-liquid interface to this zone during crystal growth, and exist in this zone by assembling the dislocation loop that interstitial atom forms.Being not easy to take place oxygen in the I zone separates out; Therefore, contain in the annealed wafer of base material in I zone, form the low density zone of oxygen precipitate in use.
According to conventional knowledge, the defect area of base material be the crystal growth condition by nitrogen concentration and V/G measure (wherein, V: rate of extension (mm/ minute), G: the average temperature gradient from fusing point to 1350 ℃ on the crystal growth direction of principal axis (℃/mm)) (V.V.Voronkov, K.CrystalGrowth, 59 (1982) 625, and M.Iida, W.Kusaki, M.Tamatsuka, E.Iino, M.Kimura and S.Muraoka, Defect in Silicon, ed.T.Abe, W.M.Bullisetal (ECS., Pennington N.J., 1999) 499).
Under the situation of the silicon single-crystal of the nitrogen that never mixes cutting base material, during greater than particular value, excessively introduced atom vacancy, and in base material, formed V zone or OSF zone at V/G.During less than particular value, excessively introduce interstitial atom at V/G, and in base material, formed the I zone.Simultaneously, nitrogen has influenced from the atom vacancy of solid-liquid interface introducing and the quantity of interstitial atom.Therefore, shown in Fig. 1 (a), may be displayed on the two-dimensional defect areal map from the defect area of the base material of nitrating silicon single-crystal cutting, wherein nitrogen concentration and V/G are as two axles.
Shown in Fig. 1 (a), in nitrogen concentration and V/G figure, a nitrating crystal ingot has certain width in nitrogen concentration and V/G, and is shown as rectangular area (being called " growth conditions zone ").This be because, shown in Fig. 1 (b), the part in the nitrating crystalline ingot 200 is low more, then nitrogen concentration is high more, and compare V/G with centre portions lower in the crystal periphery part.
Adding nitrogen in the CZ silicon single-crystal is to use the nitrating molten mass to carry out; Yet known per-cent (segregation coefficient) from molten mass introducing crystalline nitrogen concentration is very little when solidifying.Therefore, the nitrogen of the overwhelming majority is retained in the molten mass in the molten mass, and the nitrogen concentration in the molten mass increases along with the crystal growth process.Therefore, crystalline uprises than the nitrogen concentration in the lower part.Simultaneously, the average temperature gradient G on the crystal growth direction of principal axis from fusing point to 1350 ℃ (℃/mm) depend on the crystal cooling power; Yet G is bigger in the crystal periphery part, because the crystal periphery part is cooled usually easily.Therefore, V/G is lower in the crystal periphery part.
When the growth conditions scope of a nitrating crystal ingot and nitrogen concentration wherein and V/G are overlapping as the two-dimensional defect areal map of two axles, the crystalline defect area can be described.For example, in the crystal of the growth conditions scope that shows in Fig. 1 (a), the V zone is present in the germ nucleus side, and the OSF zone is present in the crystal periphery part.Fix and V/G when increasing in the nitrogen concentration scope, cavitation area expands to whole substrate surface.When V/G reduced, cavitation area was retracted to the base material center, and the I zone spreading is to whole substrate surface.Fix and nitrogen concentration when increasing at V/G, the OSF zone generates and expands to whole substrate surface from peripheral portion.
Studied the relation between the defect area in paddy zone and the base material of separating out in the annealed wafer; Found that shown in Fig. 2 (a) and 2 (b), separate out paddy zone and have closely with defect area in the base material and get in touch.Particularly, what generate annealed wafer in the position corresponding with the V zone iimit of base material separates out the paddy zone, and should expand to V area side and OSF area side slightly in the zone.
Fig. 2 (a) shows the figure that concerns between nitrogen concentration and the V/G.In the figure, in growth conditions zone 1, nitrogen concentration is 5 * 10 13To 1 * 10 14Atom/cm 3, and V/G (relative value) is 1.3 to 2.1; In growth conditions zone 2, nitrogen concentration is 1 * 10 14To 5 * 10 14Atom/cm 3, and V/G (relative value) is 1.3 to 2.1; In growth conditions zone 3, nitrogen concentration is 1 * 10 15To 5 * 10 15Atom/cm 3, and V/G (relative value) is 1.3 to 2.1; And in growth conditions zone 4, nitrogen concentration is 1 * 10 15To 5 * 10 15Atom/cm 3, and V/G (relative value) is 1.0 to 0.6.
Fig. 2 (b) is the radially-arranged chart of oxygen precipitate that shows in the substrate plane, has shown also whether oxygen precipitate density is equal to or higher than 5 * 10 8/ cm 3(" O " represents that it is equal to or higher than 5 * 10 8/ cm 3, and " * " represents that it is less than 5 * 10 8/ cm 3(also identical in similar accompanying drawing hereinafter)), and whether oxygen precipitate density radial distribution deviation was equal to or less than for 0.5 (" O " represents that it is equal to or less than 0.5, and " * " represents that it is greater than 0.5 (also identical in similar accompanying drawing hereinafter)).As shown in this chart, comprise that in the growth conditions zone this oxygen precipitate density radial distribution deviation surpasses 0.5 when separating out the paddy zone.
Under the situation in the growth conditions zone 4 of Fig. 2 (a), do not separate out the paddy zone because do not comprise in the base material, so can reach 0.5 or littler oxygen precipitate density radial distribution deviation.Yet in order to satisfy these conditions, V/G must reduce, and in other words, crystal rate of extension V must reduce.Because turnout will descend, not preferred in manufacturing processed so reduce crystal rate of extension V.
As mentioned above, in routine was created conditions, the radially inhomogeneity V/G scope of the precipitate density that can reach was extremely narrow, and this is actually inconvenient.Therefore, can reach creating conditions of the radially inhomogeneity V/G scope of precipitate density in order to find to expand, research work concentrates on the crystal growth parameter except nitrogen concentration and V/G.The crystal rate of cooling that found that during crystal growth 1100 ℃ to 1000 ℃ is set to 4 ℃/minute or the higher oxygen precipitate radial distribution that influences.
Fig. 3 (a) and 3 (b) are the synoptic diagram that is used to explain the condition of making annealed wafer, and the oxygen precipitate is uniform in this annealed wafer.Fig. 3 (a) shows the figure that concerns between nitrogen concentration and the V/G, and Fig. 3 (b) is the chart that display defect distributes, and has shown also whether oxygen precipitate density is equal to or higher than 5 * 10 8/ cm 3, and whether oxygen precipitate density radial distribution deviation is equal to or less than 0.5.Shown in growth conditions zone 5 in, nitrogen concentration is 1 * 10 14To 5 * 10 14Atom/cm 3, and V/G (relative value) is 1.3 to 1.5.At this, the NF zone among Fig. 3 (a) is the new defect area of finding between V zone iimit and OSF zone iimit.Be 4 ℃/minute or find this zone first when higher in 1100 to 1000 ℃ crystal rate of cooling during the crystal growth, and this zone is the zone that does not contain OSF and hole.
Obviously find out from the contrast between Fig. 2 and Fig. 3: 1100 to 1000 ℃ crystal rate of cooling is 4 ℃/minute or when higher, the boundary position in OSF zone does not change, and lower nitrogen and high V/G side are transferred in the border in V zone.Therefore, find that the nitrogen concentration of the usefulness for homogenizing oxygen precipitate radial distribution and the scope of V/G are extended to low nitrogen and high V/G side.
In the growth conditions of Fig. 3 (a) zone 3 and 5, though there is part beyond the OSF zone, the radial distribution of oxygen precipitate is uniformly, because separate out in the paddy zone is not included in.In other words, the distribution in oxygen precipitate radial distribution and OSF zone is irrelevant.Under the situation in growth conditions zone 5, can realize radially homogeneity of precipitate by the base material that does not contain the OSF zone.
According to conventional knowledge, for example in Japanese patent application Te Open 2003-59932, only relation between defect area and the oxygen precipitate density distribution has been discussed with regard to the relation in OSF zone.Therefore, only there is following idea in the document: this OSF zone must be controlled with control oxygen precipitate radial distribution.Yet result of study finds, as new knowledge, real important for control oxygen precipitate radial distribution is not the OSF zone, but control relevant with the V areal distribution separate out the paddy zone.
Because the nitrogen concentration range expansion is to low nitrogen side, so the nitrogen concentration scope has been expanded.Therefore, oxygen precipitate density can be controlled on a large scale according to device user's requirement.Because V/G expands to high V/G side, the output of silicon single-crystal can improve, because rate of extension V further increases.
Shown in Fig. 3 (a), oxygen precipitate density radial distribution deviation be equal to or less than 0.5 V/G scope separate out the paddy zone than lower boundary and I zone iimit between.Be summarised in a time-out in different test-results, above-mentioned V/G scope can be represented as the function of nitrogen concentration.Particularly, V/G higher limit (mm 2/ ℃ minute) be 1.6 * exp (1.0 * 10 -15* nitrogen concentration (atom/cm 3)) * (V/G) standard, and V/G lower value (mm 2/ ℃ minute) be exp (7.1 * 10 -16* nitrogen concentration (atom/cm 3)) * (V/G) standard (wherein, (V/G) standard is a V/G value corresponding to the part of the V in the silicon single-crystal that does not add nitrogen zone and I zone iimit.)
The radially-arranged relation in hole that the oxygen of base material is separated out radial distribution and base material is as follows.Fig. 4 (a) and 4 (b) explain hole radial distribution and the radially-arranged figure of oxygen precipitate.Fig. 4 (a) shows the figure that concerns between nitrogen concentration and the V/G, and Fig. 4 (b) comprises the figure that shows the hole density result, and directly upwards measuring at base material in A, B and C zone respectively of these holes is of a size of 50 to 150nm.
In the a-quadrant of Fig. 4 (a), nitrogen concentration is 1 * 10 14Atom/cm 3, and V/G (relative value) is 1.3 to 2.1; In the B zone, nitrogen concentration is 5 * 10 14Atom/cm 3, and V/G (relative value) is 1.3 to 2.1; And in the C zone, nitrogen concentration is 5 * 10 15Atom/cm 3, and V/G (relative value) is 1.3 to 2.1.
As shown in these figures, find that separate out the paddy zone is following zone: wherein being of a size of the density range that 50 to 150nm hole is present in the base material is 10 4To 2 * 10 5/ cm 3At this, the hole size is represented by the diameter of the spheroid with volume identical with the hole average-volume.The maximum value that is the hole size in separating out the paddy zone is 150nm or bigger, and the density that perhaps is of a size of 50 to 150nm hole surpasses 2 * 10 5/ cm 3The zone.Separating out the paddy zone is that the hole size is equal to or less than 50nm in addition, and perhaps hole density is less than 10 4/ cm 3The zone.Separating out the inside and outside of paddy zone, oxygen precipitate density is all greater than separating out the paddy zone.
The density range that wherein is of a size of 50 to 150nm hole is 10 4To 2 * 10 5/ cm 3The oxygen precipitate density in zone be unknown less than the reason of its peripheral region.When in about 1100 ℃ temperature range, assembling during the crystal growth, form these holes at atom vacancy; Yet the residue atom vacancy that is not gathered into the hole may be as the nuclear of the oxygen precipitate in the lower temperature range during the crystal growth (about 1000 ℃).The density range that expectation wherein is of a size of 50 to 150nm hole is 10 4To 2 * 10 5/ cm 3The zone be in following state: the concentration that wherein remains the room is minimum according to other mechanism.
The reason of separating out the paddy zone that changes in the substrate plane by the crystal rate of cooling that improves 1100 to 1000 ℃ may be that the radial distribution of hole density has been changed by 1100 to 1000 ℃ quick cooling.
May be because underlying cause, in the CZ method in the crystal growth crystal rate of cooling in 1100 to 1000 ℃ the temperature range caused the moving of paddy zone of separating out shown in Figure 4.
The oversaturated atom vacancy of introducing from solid-liquid interface is assembled down in about 1100 ℃ when crystal growth, thereby forms the hole.When 1100 to 1000 ℃ crystal rate of cooling are high, atom vacancy accumulative deficiency of time, and hole size decreases.The result is, wherein being presented at the density range that is of a size of 50 to 150nm hole among the nitrogen concentration V/G figure is 10 4To 2 * 10 5/ cm 3The zone be moved.Shown in Fig. 3 a, in the NF zone between V zone and OSF zone, may exist to be of a size of 50nm or littler hole.
Set forth the specific embodiments that silicon single-crystal manufacturing and annealed wafer are made below.
As the silicon single-crystal manufacture method, the molten mass stretching crystalline from the crucible CZ method of growing crystal simultaneously is widely used.In this silicon single-crystal manufacture method, at first polysilicon is put into the crucible of making as raw material by quartz, and with this raw material by around its well heater (structure in the stove such as well heater and thermal insulation material is called the hot-zone in the lump) fusion.Then, crystal seed is put down from the molten mass top in the crucible, and contact with the molten mass surface.In this crystal seed of rotation and control stretching speed V, make single crystal with predetermined diameter by the crystal seed that upwards stretches.When crystal growth, the silicon molten mass reduces; And, in view of the above, change such as thermal conduction in the silicon molten mass and mobile environment of crystal growth.Thereby, different being provided with added in the actual crystal manufacturing step for by keeping the constant stable crystal growth of these environment as much as possible.For example, usually according to the tensile crystal weight and the position of pull-up crucible, thereby make the silicon molten mass surface during crystal stretches keep constant with respect to the position of well heater.To compare with the fusion side be minimum in the variation of the thermal conduction condition of crystal side in the crystal growing process, and should change usually and determined by furnace structure in the stove and hot zone structure, and this changes according to crystal length and minor alteration lentamente.
Generally speaking, the thermograde G in crystal growth interface is uneven in crystallographic plane.The thermograde of the crystal side in crystal growth interface is bigger than germ nucleus part in the crystal periphery part.This is cooled off by the radiation cooling of crystal side surface because the crystal side surface is easier.Therefore, even under identical rate of extension V, V/G partly becomes lower in crystal periphery, and causes that the OSF zone that the epitaxial film defective produces partly generates in crystal periphery easily.Strictly by repetition test measure the crystal side thermograde G on the crystal draw direction in crystal growth interface, in these trials, for example crystal growth is actually by inserting in crystal and thermoelectricly carries out occasionally.
The V/G of crystal growth interface and 1100 to 1000 ℃ crystal rate of cooling during crystal growth can be respectively controlled by the G in the temperature range that changes G in the solid-liquid interface and 1100 to 1000 ℃; Yet in order to control them independently, the structure of stretching furnace must change.
In order to reduce V/G, rate of extension must reduce; Yet the result is that 1100 to 1000 ℃ crystal rate of cooling also reduces during crystal growth.Therefore,, be increased in during the crystal growth 1100 to 1000 ℃ crystal rate of cooling simultaneously, require such as the special processing that increases with the cooling power of the hot baffle placed around this crystalline mode in order to reduce the V/G on crystal growth border.
In order to make the CZ silicon single-crystal of doping nitrogen, for example be present in the method for introducing nitrogen during the raw materials melt, perhaps during raw materials melt, nitride introduced method in the sedimentary silicon substrate by CVD method etc.Segregation coefficient k corresponding to the speed in the impurity introducing crystal of concentration in the molten mass after solidifying is 7 * 10 under the situation of nitrogen -4(W.Zulehner and D.Huber, CrystalGrowth, Properties and Applications, p28, Springer-Verlag, New York, 1982).
Introduce the crystalline nitrogen concentration from molten mass and can be expressed as following expression formula: g=crystalline (weight of silicon metal) this moment/(initial molten mass weight) by using solidification rate g.(nitrogen concentration in the crystal)=k * (initial molten mass nitrogen concentration) * (1-g) K-1
How this relation all keeps constant regardless of the condition such as stretching furnace structure and rate of extension usually; Therefore, the control of the nitrogen concentration in the crystal can be controlled uniquely by the nitrogen concentration in the initial molten mass usually.
In process, use quartzy as crucible according to CZ manufactured silicon single-crystal.This quartz crucible is little by little incorporated in the silicon molten mass during crystal stretches; Therefore, oxygen is present in the silicon molten mass.From quartz crucible fused oxygen because the flowing and diffusion and moving of silicon molten mass, and the oxygen of the overwhelming majority from the molten mass surface form with SiO gas evaporate.Yet a part of oxygen is introduced in the crystal.At high temperature the oxygen of Yin Ruing is oversaturated in crystal cooling processing, therefore causes in crystal cooling period and assembles and form small oxygen cluster.These clusters are as separating out nuclear, after it is made the silicon single-crystal wafer in the device heat treatment process with SiO xForm separate out and form the oxygen precipitate.
The base material that is used for annealed wafer makes from the silicon single crystal ingot of gained.Generally speaking, use scroll saw or inner blade slicing machine cutting silicon single-crystal, and make base material by chamfering, etching and bright finished step.When extra being used to of needs adding promotes that the heat treatment step of defective is separated out or eliminated to oxygen, implement heat treatment process usually after this.Yet under the situation of the base material described in the present invention who adds nitrogen, this step is unwanted, and it can make in the step identical with general silicon substrate.
Implementing the annealed heat treatment furnace can be the stove that is purchased, and does not have mandatory provision.Yet it must be provided with as follows: sull during heating treatment can not rise to and be equal to or greater than 2nm.This is that the defective contraction/elimination during the annealing has been prevented from because when sull adheres to from the teeth outwards.Particularly, require to be provided with as follows: during heating treatment reduce the amount of the impurity of introducing atmosphere gas as much as possible, perhaps when inserting wafer in the stove, reduce the inclusion of the air of peripheral region as much as possible.Used atmosphere gas is preferably the rare gas such as argon gas, and wherein for example impurity is controlled in 5ppma or still less.
Use quartz etc. are as the assembly of supporting wafers.These assemblies raise in annealing temperature and significantly worsen when too much.Therefore, they must frequent replacement, and this is the factor that cost rises.Annealing temperature is preferably 1250 ℃ or lower.Reduce when too much in annealing temperature, the contraction rate of defective is slack-off; Therefore, the elimination process is consuming time, and reduces productive rate.Annealing temperature is preferably 1150 ℃ or higher.At annealing time in short-term, defective is retained in the substrate surface, because at annealing time in short-term, can't eliminate defective fully.When annealing time was long, productive rate descended, and once anneals the required time because prolonged.Therefore, annealing time is preferably more than and equaled 10 minutes and smaller or equal to 2 hours.
Separate out nuclear because the effect of nitrogen is heat-staple as the oxygen that forms in the nitrating base material of base material, even and also can not be eliminated during at elevated temperature fast during the annealing steps.Sometimes during annealing steps, implement to be used to promote oxygen to separate out or eliminate the extra heat treatment step of defective.In the case, before annealing steps, implement thermal treatment being lower than under the temperature of annealing steps.Yet, when adding this extra step in this way, prolonged the time of whole annealing steps; Therefore, productive rate reduces, and manufacturing cost increases.In this, under the situation of described in the present invention nitrating base material, this step is unwanted.
Embodiment
The silicon single-crystal manufacturing equipment that is used for present embodiment is the equipment that is used for according to the general silicon single-crystal manufacturing of CZ method.These equipment are to improve 1100 to 1000 ℃ first stretching furnace of rate of cooling and second stretching furnace with general rate of cooling with special methods cooling hot baffle.When enforcement is of the present invention,, then there is not particular restriction for stretching furnace as long as growth conditions of the present invention can be implemented.
Use the silicon single-crystal of these equipment growths to have following conduction type: p type (boron-doping) and crystal diameter: 8 inches (200mm).
Doping nitrogen is to put into the silicon molten mass by the base material that will have nitride film to implement.
The V/G relative value defines as follows.In the stretching furnace identical with the crystalline furnace structure of the interpolation nitrogen that wherein stretches, with different rate of extension V the crystal that does not add nitrogen and carbon is stretched, the radial distribution of distribution pit is checked by method described later, and obtains the boundary position in I zone.For example when rate of extension was low, the Waffer edge side was in the I zone, and the dislocation pit produces herein.In this case, distribute in the plane of check dislocation pit, the dislocation pit corrosion density is less than 10/cm 2Set positions be the border in I zone.The V/G value of this position is set at (V/G) standard, and the crystalline V/G relative value of tensile interpolation nitrogen is set at (V/G)/(V/G) standard in the stretching furnace of same structure.In other words, be 1 o'clock in the V/G relative value, V/G equals (V/G) standard.
The crystal that does not add nitrogen is pulled out from first stretching furnace and second stretching furnace.Obtain the V/G relative value, and produce nitrogen concentration-V/G figure.
As 1100 to 1000 ℃ rate of cooling during the crystal growth, the minimum value of thermograde on the crystal growth direction of principal axis in 1100 to 1000 ℃ scope be G2 (℃/mm) time, calculate V * G2, and as typical value.
Same area cutting base material (silicon wafer) from monocrystalline is implemented annealing, thereby is produced annealed wafer after mirror finish.
From annealed wafer sampling and implement polishing 20 μ m, use secondary ion mass spectrometry(SIMS) (SIMS) to measure nitrogen concentration to remove after the outside diffusion layer of its surperficial nitrogen.
In the V zone of base material, during crystal growth, introduce excessive atom vacancy, and produce the hole thus from solid-liquid interface.Therefore, the V zone of base material can accurately be determined by hole density.
About the hole in the base material, the LSTD scanner (MO-6) that uses Mitsui Mining and Smelting company limited to produce is measured the hole radial distribution of base material, and this scanner is commercially available defect estimation equipment.MO-6 is from Brewster angle emission visible laser, and the photographic camera that passes through to place is in vertical direction surveyed p polar dispersion image as defect image.Because laser only can infiltrate into 5 μ m from substrate surface, so can measure the degree of depth apart from substrate surface 5 μ m with interior defective.During measurement, adjust detectivity, be of a size of 50nm or bigger hole when being transformed into sphere thereby can measure.The volume density in hole is calculated by the area density in survey hole and the 5 μ m that fathom.Then, the volume density in hole is equal to or greater than 1 * 10 5/ cm 3The zone be confirmed as the V zone.
Simultaneously, in the I zone of base material, introduce excessive interstitial atom from solid-liquid interface during crystal growth, the result is that they show as the dislocation pit.Therefore, the I zone can be determined by the density of dislocation pit.
Measure the dislocation pit according to following method.At first, etch away base material 5 μ m, calculate in surface formation by observation by light microscope and be of a size of 1 μ m or the bigger rhombus or the number of streamlining dislocation pit with the Wright etching solution.Footpath at base material is upwards measured in 10mm point place, calculates dislocation pit area density by the visibility region area.Then, be 10/cm with the dislocation pit corrosion density 2Or bigger zone is defined as the I zone.
Carry out the OSF assessment of base material according to following method.At first, base material was implemented oxide treatment 1 hour down in 1100 ℃ in containing the oxygen atmosphere of steam.Then, after sull is removed by hydrofluoric acid, etch away amount, the ellipse, lune or the bar-shaped OSF pit that form from the teeth outwards with observation by light microscope corresponding to the thickness of 5 μ m with the Wright etching solution.By opticmicroscope sweep diameter on the substrate diameter direction is the number that the visibility region of 2.5 μ m calculates the OSF pit, obtains OSF area density (pit/cm by the number with the OSF pit divided by the observation area 2).The OSF area density is equal to or greater than 100/cm 2The zone be defined as the OSF zone.
Carry out the oxygen of annealed wafer according to following method and separate out characteristic evaluation.At first, with annealed wafer 780 ℃ following 3 hours and implemented twice thermal treatment in following 16 hours at 1000 ℃.Then, this wafer is rived, the BMD analyser MO-4 that utilizes Mitsui Mining and Smelting company limited to produce measures inner oxygen precipitate density.The position of measurement point is positioned at from the base material center to the point of distance edge 10mm in the plane.Obtain the minimum value of gained oxygen precipitate density and the oxygen precipitate density radial distribution deviation of representing by following expression formula.
Oxygen precipitate density radial distribution deviation=(oxygen precipitate density maximum value-oxygen precipitate density minimum value)/oxygen precipitate density maximum value
The assessment result that comprises Comparative Examples is shown in Table 1.
Table 1
Base material nitrogen concentration (atom/cm 3) Stretching furnace Rate of extension (mm/ minute) V/G relative value scope 1100 to 1000 ℃ of rate of cooling (℃/minute) (V/G) 1 (V/G) 2 Precipitate density minimum value (/cm 3) Deviation in the precipitate density plane Remarks
5.0E+14 1 1.5 1.3～2.1 8.0 0.70 2.64 1.0E+09 0.2 Embodiment 1
2.0E+15 1 1.5 1.3～2.1 8.0 0.24 11.82 4.0E+09 0.3 Embodiment 2
4.0E+15 1 1.5 1.3～2.1 8.0 0.06 87.36 9.0E+09 0.2 Embodiment 3
1.0E+15 1 0.8 0.6～1.0 4.0 0.49 4.35 2.0E+09 0.1 Embodiment 4
3.0E+15 1 0.8 0.6～1.0 4.0 0.12 32.14 4.0E+09 0.1 Embodiment 5
5.0E+15 1 0.8 0.6～1.0 4.0 0.03 237.46 9.0E+09 0.2 Embodiment 6
1.0E+14 1 1.0 1.3～1.5 5.0 0.93 1.77 5.0E+08 0.2 Embodiment 7
2.0E+14 1 1.0 1.3～1.5 5.0 0.87 1.95 6.0E+08 0.3 Embodiment 8
5.0E+14 1 1.0 1.3～1.5 5.0 0.70 2.64 1.0E+09 0.2 Embodiment 9
1.0E+14 1 0.8 1.0～1.2 4.0 0.93 1.77 5.0E+08 0.1 Embodiment 10
2.0E+14 1 0.8 1.0～1.2 4.0 0.87 1.95 7.0E+08 0.2 Embodiment 11
5.0E+14 1 0.8 1.0～1.2 4.0 0.70 2.64 1.0E+09 0.1 Embodiment 12
5.0E+13 1 0.8 1.3～2.1 4.0 0.97 1.68 1.0E+08 0.9 Comparative Examples 1
1.0E+14 1 0.8 0.6～1.0 4.0 0.93 1.77 5.0E+08 0.6 Comparative Examples 2
1.0E+14 1 1.5 1.3～2.1 4.0 0.93 1.77 5.0E+08 0.7 Comparative Examples 3
1.0E+15 2 1.2 1.3～2.1 1.0 0.49 4.35 1.0E+09 0.8 Comparative Examples 4
(V/G) 1: exp (7.1 * 10 -16* nitrogen concentration [atom/cm 3])
(V/G) 2: 1.6 * exp (1.0 * 10 -15* nitrogen concentration [atom/cm 3])
At this, (V/G) 1(V/G) 2Be respectively V/G lower value and V/G higher limit, they obtain from stretching crystalline nitrogen concentration by using corresponding expression formula.
This annealed wafer satisfies following condition: the base material nitrogen concentration is more than or equal to 5 * 10 14Atom/cm 3And smaller or equal to 5 * 10 15Atom/cm 3, and the scope of V/G relative value is more than or equal to exp (7.1 * 10 -16* nitrogen concentration (atom/cm 3)) and smaller or equal to 1.6 * exp (1.0 * 10 -15* nitrogen concentration (atom/cm 3)), and 1100 to 1000 ℃ of rate of cooling of the base material that adopts are equal to or greater than 4 ℃/minute, oxygen precipitate density minimum value is 5 * 10 8/ cm 3Or bigger, and oxygen precipitate density radial distribution deviation is 0.5 or littler, its oxygen precipitate radial distribution is good.Implement base material before the annealing and do not comprise V zone and I zone, and not have the density range that is of a size of 50 to 150nm hole in the base material be 10 as defect area 4To 2 * 10 5/ cm 3The zone.
In these embodiments, from the base material (base material of the annealed wafer of embodiment 1 to 3) of following crystal-cut, do not have OSF: at nitrogen concentration more than or equal to 5 * 10 14Atom/cm 3And smaller or equal to 4 * 10 15Atom/cm 3And the V/G relative value is more than or equal to 1.3 and smaller or equal to 2.1 o'clock, is this crystal that stretches under 8 ℃/minute the situation 1100 to 1000 ℃ rate of cooling by using first stretching furnace; And from the base material (base material of the annealed wafer of embodiment 7 to 9) of following crystal-cut, do not have OSF: at nitrogen concentration more than or equal to 1 * 10 14Atom/cm 3And smaller or equal to 5 * 10 14Atom/cm 3And the V/G relative value is more than or equal to 1.3 and smaller or equal to 1.5 o'clock, is this crystal that stretches under 5 ℃/minute the situation 1100 to 1000 ℃ rate of cooling.
The base material nitrogen concentration is less than 1 * 10 14Atom/cm 3The oxygen precipitate density minimum value of annealed wafer less than 5 * 10 8/ cm 3, and oxygen is separated out quality and is inferior to embodiments of the invention (Comparative Examples 1).
In the minimum value of V/G relative value less than exp (7.1 * 10 -16* nitrogen concentration (atom/cm 3)) time, the I zone is present in the base material; Therefore, oxygen precipitate density radial distribution deviation surpasses 0.5, and oxygen is separated out quality and is inferior to embodiments of the invention (Comparative Examples 2).
In the maximum value of V/G relative value greater than 1.6exp (1.0 * 10 -15* nitrogen concentration (atom/cm 3)) time, separate out the paddy zone and be present in the base material; Therefore, oxygen precipitate density radial distribution deviation surpasses 0.5, and oxygen is separated out quality and is inferior to embodiments of the invention (Comparative Examples 3).
, separate out the paddy zone and be present in the base material during less than 4 ℃/minute 1100 to 1000 ℃ rate of cooling, oxygen precipitate density radial distribution deviation surpasses 0.5, and oxygen is separated out quality and is inferior to embodiments of the invention (Comparative Examples 4).
Specific embodiments of the present invention and embodiment have above been set forth.Yet the present invention is not limited to these embodiment and specific embodiments, and those skilled in the art can carry out various changes, and these amended specific embodiments and embodiment still comprise technological thought of the present invention.Therefore, technology category of the present invention is only determined according to the specified note of invention of the claim of being supported by above-mentioned explanation.

Claims (4)

1, have the annealed wafer of the layer that do not contain surface imperfection and excellent absorption ability in the entire wafer surface, wherein the minimum value of oxygen precipitate density is 5 * 10 in this annealed wafer plane 8/ cm 3Or higher, and oxygen precipitate density radial distribution deviation is 0.5 or littler.
2, be used to make the method for annealed wafer, it comprises annealing silicon single-crystal base material, and this base material does not comprise V zone as defect area, and (volume density that wherein is of a size of 50nm or bigger hole is 1 * 10 5/ cm 3Or higher zone) and (density that wherein is of a size of 1 μ m or bigger dislocation pit is 10/cm in the I zone 2And do not comprise wherein the hole and be of a size of 50nm to 150nm and this hole density or higher zone), more than or equal to 10 4/ cm 3And smaller or equal to 10 5/ cm 3The zone.
3, the method that is used to make annealed wafer according to claim 2, wherein silicon single-crystal is grown in the following scope as crystal growth condition during by Czochralski manufactured silicon single-crystal:
V/G higher limit (mm 2/ ℃ minute) be 1.6 * exp (1.0 * 10 -15* nitrogen concentration (atom/cm 3)) * (V/G) standard; And V/G lower value (mm 2/ ℃ minute) be exp (7.1 * 10 -16* nitrogen concentration (atom/cm 3)) * (V/G) standard is (wherein, V is rate of extension (mm/ minute), G be on the crystal growth direction of principal axis the average temperature gradient from fusing point to 1350 ℃ (℃/mm), (V/G) standard is the lower value that does not comprise as the V/G in the I zone of not adding the defect area in the silicon single-crystal of nitrogen, and wherein said I zone is that interstitial atom excessive during crystal growth is introduced wherein and the zone that produces the dislocation pit from solid-liquid interface);
From the silicon single-crystal cutting base material of the growth of adding nitrogen, the nitrogen concentration in this silicon single-crystal is more than or equal to 1 * 10 14Atom/cm 3And smaller or equal to 5 * 10 15Atom/cm 3, and as base material; And
To described base material impurity be in 5ppm or the lower rare gas or in nonoxidizing atmosphere in more than or equal to 1150 ℃ and implement thermal treatments more than or equal to 10 minutes and smaller or equal to 2 hours smaller or equal to 1250 ℃, wherein the thickness of sull is controlled in 2nm or lower after this thermal treatment.
4, the method that is used to make annealed wafer according to claim 3 wherein by the crystal growth condition during the Czochralski manufactured silicon single-crystal is: 1100 to 1000 ℃ rate of cooling is 4 ℃/minute or faster.
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CN111430236B (en) * 2020-05-06 2021-05-14 合肥晶合集成电路股份有限公司 Wafer annealing method

Family Cites Families (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5593494A (en) * 1995-03-14 1997-01-14 Memc Electronic Materials, Inc. Precision controlled precipitation of oxygen in silicon
DE19637182A1 (en) * 1996-09-12 1998-03-19 Wacker Siltronic Halbleitermat Process for the production of silicon wafers with low defect density
JPH1179889A (en) * 1997-07-09 1999-03-23 Shin Etsu Handotai Co Ltd Production of and production unit for silicon single crystal with few crystal defect, and silicon single crystal and silicon wafer produced thereby
EP1035234A4 (en) * 1997-08-26 2003-05-28 Sumitomo Mitsubishi Silicon High-quality silicon single crystal and method of producing the same
JP3011178B2 (en) * 1998-01-06 2000-02-21 住友金属工業株式会社 Semiconductor silicon wafer, its manufacturing method and heat treatment apparatus
TW589415B (en) * 1998-03-09 2004-06-01 Shinetsu Handotai Kk Method for producing silicon single crystal wafer and silicon single crystal wafer
WO1999057344A1 (en) * 1998-05-01 1999-11-11 Nippon Steel Corporation Silicon semiconductor wafer and method for producing the same
JP4084902B2 (en) * 1998-05-01 2008-04-30 シルトロニック・ジャパン株式会社 Silicon semiconductor substrate and manufacturing method thereof
US6077343A (en) * 1998-06-04 2000-06-20 Shin-Etsu Handotai Co., Ltd. Silicon single crystal wafer having few defects wherein nitrogen is doped and a method for producing it
US6284384B1 (en) * 1998-12-09 2001-09-04 Memc Electronic Materials, Inc. Epitaxial silicon wafer with intrinsic gettering
JP3988307B2 (en) * 1999-03-26 2007-10-10 株式会社Ｓｕｍｃｏ Silicon single crystal, silicon wafer and epitaxial wafer
US20020142170A1 (en) * 1999-07-28 2002-10-03 Sumitomo Metal Industries, Ltd. Silicon single crystal, silicon wafer, and epitaxial wafer
WO2001027362A1 (en) * 1999-10-15 2001-04-19 Shin-Etsu Handotai Co., Ltd. Silicon single-crystal wafer for epitaxial wafer, epitaxial wafer, methods for producing them, and evaluating method
JP3787472B2 (en) 1999-11-12 2006-06-21 信越半導体株式会社 Silicon wafer, method for manufacturing the same, and method for evaluating silicon wafer
JP3565205B2 (en) * 2000-01-25 2004-09-15 信越半導体株式会社 Method for determining conditions for manufacturing silicon wafer and silicon single crystal and method for manufacturing silicon wafer
JP3846627B2 (en) * 2000-04-14 2006-11-15 信越半導体株式会社 Silicon wafer, silicon epitaxial wafer, annealed wafer, and manufacturing method thereof
US6835245B2 (en) * 2000-06-22 2004-12-28 Sumitomo Mitsubishi Silicon Corporation Method of manufacturing epitaxial wafer and method of producing single crystal as material therefor
KR100917087B1 (en) 2000-09-19 2009-09-15 엠이엠씨 일렉트로닉 머티리얼즈 인코포레이티드 Nitrogen-doped silicon substantially free of oxidation induced stacking faults
JP2002093814A (en) * 2000-09-19 2002-03-29 Memc Japan Ltd Substrate single crystal of silicon epitaxial wafer, and its manufacturing method
JP3994665B2 (en) * 2000-12-28 2007-10-24 信越半導体株式会社 Silicon single crystal wafer and method for producing silicon single crystal
JP4646440B2 (en) * 2001-05-28 2011-03-09 信越半導体株式会社 Method for manufacturing nitrogen-doped annealed wafer
JP2003029932A (en) 2001-07-18 2003-01-31 Hitachi Ltd Disk controller
JP2003059932A (en) * 2001-08-08 2003-02-28 Toshiba Ceramics Co Ltd Silicon single crystal wafer and production method therefor
JP4566478B2 (en) * 2001-08-09 2010-10-20 シルトロニック・ジャパン株式会社 Silicon semiconductor substrate and manufacturing method thereof
JP2003243404A (en) 2002-02-21 2003-08-29 Shin Etsu Handotai Co Ltd Method of manufacturing annealed wafer and annealed wafer
JP4699675B2 (en) * 2002-10-08 2011-06-15 信越半導体株式会社 Annealed wafer manufacturing method
TWI265217B (en) * 2002-11-14 2006-11-01 Komatsu Denshi Kinzoku Kk Method and device for manufacturing silicon wafer, method for manufacturing silicon single crystal, and device for pulling up silicon single crystal
JP4854917B2 (en) * 2003-03-18 2012-01-18 信越半導体株式会社 SOI wafer and manufacturing method thereof
JP4670224B2 (en) * 2003-04-01 2011-04-13 株式会社Ｓｕｍｃｏ Silicon wafer manufacturing method
JP5121139B2 (en) * 2005-12-27 2013-01-16 ジルトロニック アクチエンゲゼルシャフト Annealed wafer manufacturing method
JP4805681B2 (en) * 2006-01-12 2011-11-02 ジルトロニック アクチエンゲゼルシャフト Epitaxial wafer and method for manufacturing epitaxial wafer

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103237930A (en) * 2010-12-29 2013-08-07 硅电子股份公司 Method of manufacturing annealed wafer
CN103237930B (en) * 2010-12-29 2015-10-21 硅电子股份公司 Manufacture the method for annealed wafer
CN103173857A (en) * 2011-12-21 2013-06-26 硅电子股份公司 Silicon single crystal substrate and method of manufacturing the same
CN103173857B (en) * 2011-12-21 2015-09-30 硅电子股份公司 Silicon mono-crystalline substrate and manufacture method thereof
US9303332B2 (en) 2011-12-21 2016-04-05 Siltronic Ag Silicon single crystal substrate and method of manufacturing the same
CN105603534A (en) * 2016-02-26 2016-05-25 吕远芳 Germanium crystal stress elimination method

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